WO2022248687A1 - Procédé de condensation partielle d'un mélange de composés oxygénés - Google Patents

Procédé de condensation partielle d'un mélange de composés oxygénés Download PDF

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Publication number
WO2022248687A1
WO2022248687A1 PCT/EP2022/064449 EP2022064449W WO2022248687A1 WO 2022248687 A1 WO2022248687 A1 WO 2022248687A1 EP 2022064449 W EP2022064449 W EP 2022064449W WO 2022248687 A1 WO2022248687 A1 WO 2022248687A1
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partial condensation
formaldehyde
condensate
glycolaldehyde
vapour phase
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PCT/EP2022/064449
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English (en)
Inventor
Christian Mårup OSMUNDSEN
Lars Saaby Pedersen
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Topsoe A/S
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Priority to US18/289,966 priority Critical patent/US20240270670A1/en
Priority to CN202280035252.0A priority patent/CN117295707A/zh
Priority to AU2022281113A priority patent/AU2022281113A1/en
Priority to JP2023573122A priority patent/JP2024521177A/ja
Priority to EP22731150.3A priority patent/EP4347546A1/fr
Priority to BR112023020949A priority patent/BR112023020949A2/pt
Publication of WO2022248687A1 publication Critical patent/WO2022248687A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
    • B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/60—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in six-membered rings

Definitions

  • This present invention relates to a process for the partial condensation of an oxygenate mixture to provide a condensate having an increased glycolaldehyde to formaldehyde ratio compared to the glycolaldehyde to formaldehyde ratio of the oxygenate mixture.
  • Biomass is of particular interest as a raw material due to its potential for supplementing and possibly replacing petroleum as a feedstock for the preparation of commercial chemicals. In recent years, various technologies for exploiting biomass have been investigated.
  • Carbohydrates represent a large fraction of biomass, and various strategies for their efficient use as a feedstock for the preparation of commercial chemicals are being established. These strategies include various fermentation-based processes, pyrolysis, and other processes, such as hydrogenolysis, hydroformylation or acid catalyzed dehydration.
  • chemicals produced from biomass include: substitute natural gas, biofuels, such as ethanol and bio-diesel, food browning materials, and commercial chemicals, such as diols (ethylene glycol and propylene glycol), acids (lactic acid, acrylic acid, and levulinic acid) and a wide range of other important chemical intermediates (epichlorohydrin, isoprene, furfural, and synthesis gas).
  • oxygenate products are being developed and an increasing demand for those products are expected.
  • Such oxygenate products may e.g. be used for producing ethylene glycol and propylene glycol by subjecting the oxygenate product to hydrogenation (see, e.g., WO 2016/001169) or for scavenging hydrogen sulphide as described in WO 2017/064267.
  • hydrogenation see, e.g., WO 2016/001169
  • scavenging hydrogen sulphide as described in WO 2017/064267.
  • many other uses may be envisaged.
  • compositions consisting primarily of C1-C3 oxygenates are formed.
  • the primary C1 oxygenate is formaldehyde, which is undesirable in many products because it is highly toxic/carcinogenic, and has been shown to act as a catalyst poison (see US 2016/002137).
  • the primary C2 oxygenate is glycolaldehyde, which is a desired product as it may be converted to useful chemicals, such as ethylene glycol, glycolic acid and methylvinylglycolate.
  • Oxygenate mixtures produced from the fragmentation of carbohydrates are useful in a number of different applications, where the toxicity of formaldehyde may be a problem. Preparation of a formaldehyde free, or depleted, composition is therefore highly desirable.
  • US 2016/002137 discusses a method for removing formaldehyde by reactive distillation; however, this method adds additional process steps.
  • the gas stream from a thermal cracker is condensed to produce a single liquid product. This is performed to ensure complete condensation and no loss of product, see for example US5393542 and US7094932.
  • the condensed product is either then limited as to its application due to the content of formaldehyde, or must be subject to purification such as fractionation to remove formaldehyde to acceptable levels. Such a separation is particularly difficult with oxygenate mixtures prepared from aqueous solutions.
  • composition prepared by a process comprising the steps of
  • a composition consisting primarily of C1-C3 oxygenates is formed.
  • the product obtained by fragmentation (e.g. thermolysis) of carbohydrates also contains significant amounts of C-1 and C-3 oxygenates as well as larger molecules.
  • the presence of the C-1 oxygenate, formaldehyde is often undesired and for many applications formaldehyde removal is necessary.
  • the presence of the larger and heavier molecules in the condensate of the pyrolysis product is also undesired.
  • significant resources may be spent on fractionation by distillation of a condensed oxygenate mixture, such as a glucose based pyrolysis product. This separation may produce an oxygenate syrup rich in glycolaldehyde and free of high- boiling byproducts but is associated with an unacceptable yield loss.
  • the product of a partial condensation is a partial condensation vapour phase enriched in the lighter components (such as formaldehyde) and a partial condensation condensate, which is a liquid phase, enriched in the heavier, condensed components and in particular glycolaldehyde.
  • the numbers of condensers and the cut can be adjusted for the given process. For example, for condensation of a glucose based pyrolysis product three stages could be provided, where the high-boiling components are removed as a first partial condensation condensate, a fraction rich in C-2 oxygenates are recovered as the second partial condensation condensate, and the C-1 oxygenates and water is obtained in the third and final condensation stage.
  • the process provides for the recovery of a C-2 oxygenate fraction with better properties (higher purity) and in higher yield than what can be obtained by fractionation of a totally condensed pyrolysis product mix.
  • EP3786145 relates to a process for large scale and energy efficient production of oxygenates from sugar in which a sugar feedstock is introduced into a thermolytic fragmentation reactor comprising a fluidized stream of heat carrying particles.
  • the heat carrying particles may be separated from the fluidized stream prior to cooling the fragmentation product and may be directed to a reheater to reheat the particles and recirculate the heated particles to the fragmentation reactor.
  • the Example of EP3786145 describes a process similar to the present invention but contains a partial condensation condensate in which the mass fraction of water is from 0.51 to 0.6.
  • vapour phase oxygenate mixture obtained from fragmentation of an aqueous solution of carbohydrates. It has been found that the formation of the vapour phase oxygenate mixture obtained by fragmentation of an aqueous solution of carbohydrates may result in problems with separating formaldehyde from the oxygenate mixture. We have found that these problems may be overcome using the partial condensation process of the present invention. In particular, we found that when keeping the water concentration in the partial condensation condensate relatively low, the tendency of formaldehyde to condense may be greatly reduced. Instead, formaldehyde remains in the vapour phase and could thus be removed from the other (heavier) oxygenates. It is thus desirable that the partial condensation condensate has a low concentration of water.
  • a low concentration of water it is to be understood that some water may be bound as a glycolaldehyde hydrate.
  • the water concentration of the partial condensation condensate may be determined by the Karl- Fischer titration method. It will be appreciated by one skilled in the art that the mass fraction of water in the partial condensation condensate may be controlled by controlling the process parameters. These process parameters will depend on, among other things, the source material of the vapour phase oxygenate material, and it will be understood that multiple process parameters may be inter dependent i.e. changing one parameter will modify the optimum for one or more other process parameters. These process parameters may be readily determined and controlled by one skilled in the art.
  • the mass fraction of water in the partial condensation condensate is from 0.02 to 0.3. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.03 to 0.3. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.04 to 0.3. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.05 to 0.3. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.02 to 0.2. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.03 to 0.2. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.04 to 0.2.
  • the mass fraction of water in the partial condensation condensate is from 0.05 to 0.2. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.02 to 0.15. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.03 to 0.15. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.04 to 0.15. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.05 to 0.15. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.02 to 0.1. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.03 to 0.1. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.04 to 0.1. In one aspect, the mass fraction of water in the partial condensation condensate is from 0.05 to 0.1.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the mass fraction of glycolaldehyde in the partial condensation condensate is decreased with respect to the mass fraction of formaldehyde in the oxygenate mixture.
  • the partial condensation condensate has a mass fraction of formaldehyde decreased with respect to the mass fraction of formaldehyde in the oxygenate mixture.
  • the vapour phase oxygenate mixture will have a ratio of glycolaldehyde to formaldehyde which may vary depending on the carbohydrate feed and the conditions of the fragmentation.
  • the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 2:1 to 18:1.
  • the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 3:1 to 18:1.
  • the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 4:1 to 18:1.
  • the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 5:1 to 18:1. In one aspect, the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 2:1 to 15:1. In one aspect, the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 3:1 to 15:1. In one aspect, the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 4:1 to 15:1. In one aspect, the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 5:1 to 15:1.
  • the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 2:1 to 10:1. In one aspect, the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 3:1 to 10:1. In one aspect, the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 4:1 to 10:1. In one aspect, the vapour phase oxygenate mixture has a mass ratio of glycolaldehyde to formaldehyde of 5:1 to 10:1.
  • the partial condensation condensate has a mass fraction of formaldehyde decreased with respect to the mass fraction of formaldehyde in the oxygenate mixture.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 5:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 10:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 15:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 20:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 30:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 40:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 50:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 60:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 70:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 80:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 90:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of at least 100 1
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 500:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 400:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 300:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 200:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 180:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 160:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 150:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 140:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 130:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 120:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 110:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of no greater than 100:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 200:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 180:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 160:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 150:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 140:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 130:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 120:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 110:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 10:1 to 100:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 200:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 180:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 160:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 150:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 140:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 130:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 120:1. In one aspect, the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 130:1.
  • the partial condensation condensate has a mass ratio of glycolaldehyde to formaldehyde of from 30:1 to 100:1.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased at least 2 fold relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture would be at least 4:1.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased at least 3 fold relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased at least 4-fold relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased at least 5-fold relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture. In one aspect, the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased at least 10-fold relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture. In one aspect, the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased at least 15-fold relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased at least 20-fold relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture. Any level of increase will satisfy this requirement. However, in some aspects, it is desirable to collect in the partial condensation condensate particular proportions of the total amount of the glycolaldehyde which is present in the vapour phase oxygenate mixture. In one aspect, the partial condensation condensate contains at least 30wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture.
  • the partial condensation condensate contains at least 40wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture. In one aspect, the partial condensation condensate contains at least 50wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture. In one aspect, the partial condensation condensate contains at least 60wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture. In one aspect, the partial condensation condensate contains at least 70wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture. In one aspect, the partial condensation condensate contains at least 80wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture.
  • the partial condensation condensate contains at least 90wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture. In one aspect, the partial condensation condensate contains at least 95wt.% of the glycolaldehyde present in the vapour phase oxygenate mixture. Condensation
  • step b) performing on the vapour phase oxygenate mixture a partial condensation to provide (i) a partial condensation condensate wherein the mass ratio of glycolaldehyde to formaldehyde in the partial condensation condensate is increased relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture; and (ii) a partial condensation vapour phase.
  • the step (b) may be preceded by one or more condensation steps.
  • the step (b) may be followed by one or more condensation steps. For example, as discussed herein, multiple fractional condensations may be carried out in series. For example, a series of condensates of different compositions may be obtained.
  • the numbers of condensers and the cut can be adjusted for the given process. For example, for fractionation of a glucose based pyrolysis product three stages could be provided, where the high-boiling components are removed as a first partial condensation condensate, a fraction rich in C-2 oxygenates are recovered as the second partial condensation condensate, and the C-1 oxygenates and water is obtained in the third and final partial condensation stage.
  • the present process comprises a further step of (c) performing on the partial condensation vapour phase of step (b) a second condensation step to provide a second condensate.
  • the second condensation step is a total condensation of the partial condensation vapour phase of step (b). In one aspect, the second condensation step is a partial condensation of the partial condensation vapour phase of step (b).
  • the second condensation step is a total condensation of the partial condensation vapour phase of step (b)
  • the second condensate may have a mass fraction of formaldehyde increased with respect to the mass fraction of formaldehyde in the vapour phase oxygenate mixture.
  • the second condensation step is a total condensation of the partial condensation vapour phase of step (b)
  • the mass ratio of glycolaldehyde to formaldehyde in the second condensate is decreased relative to the mass ratio of glycolaldehyde to formaldehyde in the vapour phase oxygenate mixture.
  • the “vapour phase oxygenate mixture” may also be referred to as a “pyrolysis product”, a “pyrolysis product mix”, a “pyrolysis vapour phase” etc.
  • the present process relates to the partial condensation of an oxygenate mixture which is obtained from fragmentation of an aqueous solution of carbohydrates.
  • the fragmentation step is incorporated in the present process.
  • the present invention includes the step of fragmentation of an aqueous solution of carbohydrates to provide the vapour phase oxygenate mixture of step (a).
  • the fragmentation of the aqueous solution of carbohydrates may be achieved by any suitable means.
  • the fragmentation of the aqueous solution of carbohydrates is thermolytic fragmentation.
  • the fragmentation of the aqueous solution of carbohydrates is pyrolysis.
  • the fragmentation of the aqueous solution of carbohydrates may be performed by any suitable process. In one aspect the fragmentation of the aqueous solution of carbohydrates is performed as described in W02020/016209.
  • the carbohydrates of the aqueous solution may be any suitable carbohydrates.
  • the carbohydrates are selected from monosaccharides, disaccharides and mixtures thereof.
  • the carbohydrates are at least monosaccharides.
  • the carbohydrate is at least glucose.
  • the carbohydrates of the aqueous solution of carbohydrates comprise at least 20 wt.% monosaccharides based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 30 wt.% monosaccharides based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 40 wt.% monosaccharides based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 50 wt.% monosaccharides based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 60 wt.% monosaccharides based on the total amount of carbohydrates.
  • the carbohydrates of the aqueous solution of carbohydrates comprise at least 70 wt.% monosaccharides based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 80 wt.% monosaccharides based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 90 wt.% monosaccharides based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 95 wt.% monosaccharides based on the total amount of carbohydrates.
  • the carbohydrates of the aqueous solution of carbohydrates comprise at least 20 wt.% glucose based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 30 wt.% glucose based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 40 wt.% glucose based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 50 wt.% glucose based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 60 wt.% glucose based on the total amount of carbohydrates.
  • the carbohydrates of the aqueous solution of carbohydrates comprise at least 70 wt.% glucose based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 80 wt.% glucose based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 90 wt.% glucose based on the total amount of carbohydrates. In one aspect, the carbohydrates of the aqueous solution of carbohydrates comprise at least 95 wt.% glucose based on the total amount of carbohydrates.
  • the aqueous solution of carbohydrates may comprise carbohydrates in any suitable amount.
  • the aqueous solution of carbohydrates comprises carbohydrates in an amount of at least 10 wt.% based on the aqueous solution.
  • the aqueous solution of carbohydrates comprises carbohydrates in an amount of at least 20 wt.% based on the aqueous solution.
  • the aqueous solution of carbohydrates comprises carbohydrates in an amount of at least 30 wt.% based on the aqueous solution.
  • the aqueous solution of carbohydrates comprises carbohydrates in an amount of at least 40 wt.% based on the aqueous solution.
  • the aqueous solution of carbohydrates comprises carbohydrates in an amount of at least 50 wt.% based on the aqueous solution. In one aspect, the aqueous solution of carbohydrates comprises carbohydrates in an amount of at least 60 wt.% based on the aqueous solution. In one aspect, the aqueous solution of carbohydrates comprise glucose in an amount of at least 10 wt.% based on the aqueous solution. In one aspect, the aqueous solution of carbohydrates comprise glucose in an amount of at least 20 wt.% based on the aqueous solution. In one aspect, the aqueous solution of carbohydrates comprise glucose in an amount of at least 30 wt.% based on the aqueous solution.
  • the aqueous solution of carbohydrates comprise glucose in an amount of at least 40 wt.% based on the aqueous solution. In one aspect, the aqueous solution of carbohydrates comprise glucose in an amount of at least 50 wt.% based on the aqueous solution. In one aspect, the aqueous solution of carbohydrates comprise glucose in an amount of at least 60 wt.% based on the aqueous solution.
  • the process parameters required to perform the partial condensation of the present invention can be readily determined by one skilled in the art. Key parameters are the composition of the vapour phase oxygenate mixture, the partial condensation temperature and the partial condensation pressure. In general, the composition of the vapour phase oxygenate mixture will be defined by the fragmentation process. Similarly, the pressure of the partial condensation will typically be defined by requirements of the upstream process. Thus, the temperature of the partial condensation is the parameter typically controlled to achieve the required separation. If the pressure is not defined by upstream process considerations, and can be freely controlled, in principle this may be used as the controlling parameter instead (at a fixed temperature). However for most practical applications, controlling the temperature of the partial condensation will be more appropriate. In any case, the considerations for using the pressure as controlling parameter will be identical to those outlined below for temperature.
  • a suitable water content in the partial condensation condensate should be achieved.
  • this suitable water content will typically be 2 to 20 wt.%.
  • the water content of the partial condensation condensate can easily be determined using known analysis techniques, such as Karl-Fischer titration. If the water content of the first condensate is below the optimal value, the temperature of the partial condensation condenser should be decreased, and similarly if the water content is higher than optimal, the temperature of the partial condensation condenser should be increased.
  • the partial condensation condensate is condensed at a temperature of from 0 to 150°C. In one aspect, the partial condensation condensate is condensed at a temperature of from 10 to 150°C. In one aspect, the partial condensation condensate is condensed at a temperature of from 20 to 150°C. In one aspect, the partial condensation condensate is condensed at a temperature of from 30 to 150°C. In one aspect, the partial condensation condensate is condensed at a temperature of from 30 to 130°C. In one aspect, the partial condensation condensate is condensed at a temperature of from 0 to 90°C. In one aspect, the partial condensation condensate is condensed at a temperature of from 5 to 90°C. In one aspect, the partial condensation condensate is condensed at a temperature of from 40 to 90°C. In one aspect there is provided a process for the partial condensation of an oxygenate mixture, the process comprising the steps of
  • step (b) an intermediate step may be performed on the oxygenate mixture.
  • an initial partial condensation may be performed on the oxygenate mixture prior to the partial condensation step (b).
  • step (b) is performed on an oxygenate mixture obtained directly from fragmentation of an aqueous solution of carbohydrates.
  • This intermediate step may be selected, for example, depending on the composition of the oxygenate mixture obtained directly from fragmentation of an aqueous solution of carbohydrates.
  • the composition of the oxygenate mixture obtained directly from fragmentation of an aqueous solution of carbohydrates will depend, among other things, on the composition of the aqueous solution of carbohydrates and the fragmentation process parameters.
  • the process of the present invention may comprise one or more further steps. These one or more further steps may be before, after, or intermediate to the steps recited herein.
  • composition prepared by a process comprising the steps of
  • Sodium silicate glass beads (100 g) was loaded in a bubbling fluid bed reactor (42 mm ID) and fluidized at a superficial gas velocity of approx. 50 cm/s. The temperature was increased to 520°C, at which point a feed of water was injected into the bed. The feed was injected through a two-fluid nozzle at a rate of 2 g/min. Once the system reached steady state, the feed was switched to a 30 wt.% aqueous solution of glucose and time set as to. The gas leaving the reactor (vapour phase oxygenate mixture) was cooled (to achieve a partial condensation) in a primary condenser, and a first condensate was collected. The temperature in the primary condenser was varied between 3 and 67°C.
  • the vapour phase leaving the primary condenser was sent to a secondary condenser held at 1°C to condense the remaining condensable components as a second condensate.
  • concentrations of oxygenates in the condensates were determined by HPLC analysis, and the yield of oxygenates calculated based on the mass of collected product. Table 1 below shows results for the first liquid condensate.
  • Table 1 Data for the analysis of first liquid condensate at various temperatures.
  • the feed to the first condenser is the hot gas leaving the reactor (vapour phase oxygenate mixture).
  • Mass collected is the mass of first condensate per mass of feed fed to the bubbling fluid bed reactor.
  • the amounts of glycolaldehyde and formaldehyde, respectively, are the amounts of carbon present in glycolaldehyde and formaldehyde, respectively, in the first condensate, per total amount of carbon present in the feed fed to the bubbling fluid bed reactor.
  • Water is the percentage of water in the first condensate.
  • An aqueous solution of oxygenates produced by the method described in example 1, was evaporated.
  • the mixture contained 141 g/L of glycolaldehyde and 29 g/L of formaldehyde.
  • the evaporation was performed by feeding 0.1 g/L of oxygenate solution, together with 100 NmL/min of nitrogen, into an evaporator held at 300°C.
  • the produced gas stream (vapour phase oxygenate mixture) was directed to a primary condenser (to achieve partial condensation) maintained at a temperature from 5-90°C to collect a first condensate.
  • the vapour phase leaving the primary condenser was sent to a secondary condenser held at 1°C to condense the remaining condensable components as a second condensate.
  • the concentrations of oxygenates in the condensates were determined by HPLC analysis, and the yield of oxygenates calculated based on the mass of collected product. Table 2 below shows results for the first liquid condensate.
  • Table 2 Data for the analysis of first liquid condensate at various temperatures.
  • the feed fed to the first condenser is a vapour phase oxygenate mixture prepared by evaporation of a liquid pyrolysis product to produce the vapour phase oxygenate mixture.
  • Mass collected is the mass of first condensate per mass of oxygenate solution evaporated and fed to the primary condenser.
  • the recovery of glycolaldehyde is the percentage of the glycolaldehyde present in the vapour phase oxygenate mixture fed to the primary condenser, which was collected in the first condensate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de condensation partielle d'un mélange de composés oxygénés, le procédé comprenant les étapes consistant à (a) fournir un mélange de composés oxygénés en phase vapeur obtenu à partir de la fragmentation d'une solution aqueuse d'hydrates de carbone ; et (b) effectuer sur le mélange de composés oxygénés en phase vapeur une condensation partielle pour obtenir (i) un condensat de condensation partielle, la fraction massique d'eau dans le condensat de condensation partielle étant de 0,02 à 0,3 et le rapport massique de glycolaldéhyde au formaldéhyde dans le condensat de condensation partielle étant augmenté par rapport au rapport massique de glycolaldéhyde au formaldéhyde dans le mélange de composés oxygénés en phase vapeur ; et (ii) une phase vapeur de condensation partielle.
PCT/EP2022/064449 2021-05-28 2022-05-27 Procédé de condensation partielle d'un mélange de composés oxygénés WO2022248687A1 (fr)

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US18/289,966 US20240270670A1 (en) 2021-05-28 2022-05-27 Process for partial condensation of an oxygenate mixture
CN202280035252.0A CN117295707A (zh) 2021-05-28 2022-05-27 含氧化合物混合物的部分冷凝方法
AU2022281113A AU2022281113A1 (en) 2021-05-28 2022-05-27 Process for partial condensation of an oxygenate mixture
JP2023573122A JP2024521177A (ja) 2021-05-28 2022-05-27 含酸素化合物混合物の部分凝縮方法
EP22731150.3A EP4347546A1 (fr) 2021-05-28 2022-05-27 Procédé de condensation partielle d'un mélange de composés oxygénés
BR112023020949A BR112023020949A2 (pt) 2021-05-28 2022-05-27 Processo para condensação parcial de uma mistura de oxigenados

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BR112023020949A2 (pt) 2023-12-12
AU2022281113A1 (en) 2023-10-26
EP4347546A1 (fr) 2024-04-10
CN117295707A (zh) 2023-12-26
US20240270670A1 (en) 2024-08-15

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